Ion Microprobe Research Articles

Isotopic analyses of Ordovician–Silurian siliceous skeletons indicate silica‐depleted Paleozoic oceans

The Phanerozoic Eon marked a major transition from marine silica deposition exclusively via abiotic pathways to a system dominated by biogenic silica sedimentation. For decades, prevailing ideas predicted this abiotic-to-biogenic transition were marked by a significant decrease in the concentration of dissolved silica in seawater; however, due to the lower perceived abundance and uptake affinity of sponges and radiolarians relative to diatoms, marine dissolved silica is thought to have remained elevated above modern values until the Cenozoic radiation of diatoms. Studies of modern marine silica biomineralizers demonstrated that the Si isotope ratios (δ30 Si) of sponge spicules and planktonic silica biominerals produced by diatoms or radiolarians can be applied as quantitative proxies for past seawater dissolved silica concentrations due to differences in Si isotope fractionations among these organisms. We undertook 446 ion microprobe analyses of δ30 Si and δ18 O of sponge spicules and radiolarians from Ordovician-Silurian chert deposits of the Mount Hare Formation in Yukon, Canada. These isotopic data showed that sponges living in marine slope and basinal environments displayed small Si isotope fractionations relative to coeval radiolarians. By constructing a mathematical model of the major fluxes and reservoirs in the marine silica cycle and the physiology of silica biomineralization, we found that the concentration of dissolved silica in seawater was less than ~150μM during early Paleozoic time-a value that is significantly lower than previous estimates. We posit that the topology of the early Paleozoic marine silica cycle resembled that of modern oceans much more closely than previously assumed.

Geology and geochronology of the Archean plutonic rocks in the northeast Democratic Republic of Congo

Here we report the first regional-scale study of Archean plutonic rocks from 50,000 km2 of the northeast Democratic Republic of Congo (DRC). We include 50 new U-Pb zircon Sensitive High-Resolution Ion MicroProbe (SHRIMP) ages supported by petrographic and whole rock geochemical data from a further ~400 samples, and 39 additional U-Pb zircon ages reported by Kabete et al. (submitted) and Bird (2016).Felsic-intermediate magmatism across the northeast DRC occurred from ~ 3200 to 2530 Ma. Plutonism before ~ 2670 Ma is restricted to the West Nile Gneiss in eastern and northern-most DRC, whereas plutonism across the remainder of the northeast DRC initiated between 2670 and 2640 Ma. Two Neoproterozoic granite plutons ~ 1000–950 Ma are also present within the West Nile Gneiss. Magmatism between ~ 2670 and 2530 Ma marks the principal period of crustal growth in the northeast DRC. Felsic-intermediate plutonism between ~ 2670 and 2600 Ma included two suites of magnesian, calc-alkaline rocks, (1) a sodic-calcic suite with high Sr/Y ratios (>40) comparable with tonalite-trondhjemite-granodiorite (TTG) suites in other Archean terranes, and (2) a calc-alkaline to high-K suite of granitoids with low Sr/Y ratios (<40) and lower Na and Al contents, comparable with “low-Ca” granites in the Yilgarn Craton. In contrast, most granitoids emplaced between ~ 2600 and 2530 Ma have ferroan, high-K calc-alkaline compositions, and are enriched in high field strength (HFSE) and rare Earth elements (REE). Although the HFSE-elevated granitoids are comparable with Closepet-type, and “mafic granites” in other Neoarchean terranes, their volume within the northeast DRC appears unprecedented.Before ~ 2600 Ma partial melting of hydrous metabasalts at depths > 40 km is inferred to have produced the high Sr/Y magnesian granitoids, whereas the low Sr/Y magnesian granitoids were derived from melting-assimilation-storage-hybridization (MASH) processes in the overlying low-mid crust during the same period. Trans-lithospheric extension after ~ 2600 Ma, enabled asthenospheric mantle to interact with the base of the crust, resulting in high-temperature melting that produced the HFSE-elevated granitoids. Inherited Meso- and Paleoarchean zircons are almost completely restricted to the area within 30–40 km of the West Nile Gneiss, implying most of the northeast DRC is underlain by juvenile Neoarchean crust.

Fluorine partitioning between quadrilateral clinopyroxenes and melt

Abstract Concentrations of fluorine and chlorine were measured in glasses (quenched melts) and coexisting clinopyroxene, orthopyroxene, olivine, and plagioclase in run products of experiments previously used to measure sulfur partitioning between these phases. The partitioning of F between clinopyroxene and silicate melt was determined in 13 experiments at a variety of pressures, temperatures, and melt compositions ranging from basaltic to dacitic (49 to 66 wt% SiO2) at 0.8 to 1.2 GPa and 1000 to 1240 °C, at hydrous and anhydrous conditions. Additionally, we determined the crystal-melt partitioning of F for 4 experiments with plagioclase, 2 with orthopyroxene, and 1 with olivine. Although Cl was also measured in the experiments, the concentrations in the crystals are close to background concentration levels. The partition coefficients of fluorine between clinopyroxene and melt varied from ~0.09 to 0.29 and were linearly dependent upon the concentration of aluminum in the octahedral M1 site of clinopyroxene. Similar relationships are seen when our results are combined with previous measurements of the fluorine partition coefficient between clinopyroxene and melt, but each study shows its own unique correlation between the F partition coefficient and AlM1. These dissimilarities in correlations with AlM1 are attributed to differing analytical protocols used in the various studies. However, the combined data set demonstrates a linear correlation with AlM1, the inverse of the NBO/T ratio of the melt (T/NBO), pressure and temperature, which can be described as: l n ⁡ ( D F C p x / L ) = ( 0.2298 ± 0.04847 ) ( T / N B O ) - ( 1.029 ± 0.8045 ) ( A l M 1 ) - ( 3889 ± 1803 ) ( 1 / T ) - ( 0.5472 ± 0.1084 ) ( P ) + 0.5871 ± 1.304 , where each uncertainty is 1 standard error in the fit (as calculated by the R-project software), T is in K, and P is in GPa. Although this relationship reproduces 81% of the partitioning data to within 25% (relative), the different linear trends of the partition coefficient, DFCpx/L vs. AlM1 from different laboratories suggest the need for additional investigations and development of clinopyroxene standards with certified fluorine compositions. Nevertheless, we conclude that the self-consistency of each study indicates that F partition coefficients determined using one protocol can be applied to minerals or glasses analyzed using the same protocol and ion microprobe to better understand the storage and transport of fluorine in magmatic systems.

New interpretations of the ages and origins of the Hawkeye Granite Gneiss and Lyon Mountain Granite Gneiss, Adirondack Mountains, NY: Implications for the nature and timing of Mesoproterozoic plutonism, metamorphism, and deformation

The Hawkeye Granite Gneiss and Lyon Mountain Granite Gneiss are widespread Mesoproterozoic plutonic rocks that occur in the amphibolite- to granulite-facies Adirondack Highlands of northern New York, USA. The strongly deformed Hawkeye Granite Gneiss, previously dated by zircon multi-grain thermal ionization mass spectrometry (TIMS) U-Pb analyses at about 1100 Ma, was intruded by the weakly deformed Lyon Mountain Granite Gneiss. Previous sensitive high resolution ion microprobe (SHRIMP) analyses of Lyon Mountain Granite Gneiss zircon rims were considered to record the time of igneous emplacement at about 1.05 Ga, whereas the ages of zircon cores (~1.15 Ga) were interpreted as being inherited from nearby metaigneous country rocks. This interpretation has formed the basis of numerous models for the Mesoproterozoic structural and tectonic evolution of the Adirondacks Highlands. New U-Pb spot analyses (~15–20 µm diameter) by SHRIMP from four samples of Hawkeye Granite Gneiss and eight samples of Lyon Mountain Granite Gneiss challenge the historically accepted ages of the rocks. Using a combination of high-resolution CL imagery of oscillatory zoned cores and weakly zoned to unzoned rims, SHRIMP U-Pb geochronology, SHRIMP trace element geochemistry, and SEM petrography, we conclude that: (1) the Hawkeye Granite Gneiss was emplaced at about 1160–1155 Ma; (2) the vast majority of Lyon Mountain Granite Gneiss zircon cores yield ages of 1150–1145 Ma and are mainly primary, not inherited; and (3) the Hawkeye Granite Gneiss and Lyon Mountain Granite Gneiss zircon rims (~1080–1000 Ma) are metamorphic in origin, not igneous. Thus, both the Hawkeye Granite Gneiss and Lyon Mountain Granite Gneiss are considered herein to be late members of the mangerite-charnockite-granite (MCG) plutonic suite, emplaced during the waning stages of the Shawinigan orogeny. Zircon cores from two small plutons of largely undeformed fayalite granite of the Lyon Mountain Granite Gneiss are about 1142 Ma, providing a minimum age constraint for the termination of the Shawinigan. Zircon rim ages can be deconvoluted into multiple metamorphic events of the Ottawan and Rigolet tectonothermal events. These new interpretations have profound implications for structural, tectonic, and ore deposit models of the Adirondacks Highlands.

Petrogenesis of coeval shoshonitic and high-K calc-alkaline igneous suites in the Eopyeong granitoids, Taebaeksan Basin, South Korea: Lithospheric thinning-related Early Cretaceous magmatism in the Korean Peninsula

The Early Cretaceous was the initial period of prolonged Cretaceous-Tertiary magmatic episode in the Korean Peninsula, during which a tectonic transition from compression to extension occurred. The Early Cretaceous Eopyeong granitoids in the Taebaeksan Basin consist of two distinct series of magmas: shoshonitic and high-K calc-alkaline series. We investigated the petrology, whole-rock major and trace element geochemistry, and Sr-Nd-Pb isotope compositions of the Eopyeong granitoids to understand their magma evolution processes and source characteristics. Sensitive high-resolution ion microprobe zircon U-Pb analysis was performed on the Eopyeong granitoids to constrain their intrusion ages. Zircon U-Pb ages of the shoshonitic and high-K calc-alkaline series are 110.63 ± 0.52 and 110.65 ± 0.66 Ma, respectively, indicating that the two series formed during the same magmatic event. The mafic mineral assemblages of the shoshonitic series change from two-pyroxene+biotite to clinopyroxene+amphibole+biotite through magma evolution, whereas those of the high-K calc-alkaline series consist of more hydrous assemblages of amphibole+biotite. The shoshonitic series is also distinguished from the high-K calc-alkaline series by its higher La/Yb ratio and negative anomalies of Rb, Ba, and Eu. Mineral geothermobarometry and hygrometry data and geochemical mass balance modeling results show that the two series evolved mainly by fractional crystallization from two distinct parental magmas containing different water contents. Primitive rocks from each series have high compatible element contents such as MgO, Cr, and Ni with high Mg# compared to crustal melts in a similar range of SiO2, suggesting their mantle origin. They also have abundant incompatible elements and ‘crust-like’ isotopic compositions [(87Sr/86Sr)i = 0.7093–0.7098; εNd(t) = −7.1 to −8.8; (206Pb/204Pb)i = 18.133–18.327; (207Pb/204Pb)i = 15.621–15.665; (208Pb/204Pb)i = 38.691–38.862] with negative Nb-Ta anomalies in the primitive mantle-normalized patterns. The enrichment in both compatible and incompatible elements can be best explained by partial melting of phlogopite-bearing lithospheric mantle metasomatized by isotopically enriched upper crustal sediment-derived melt or fluid. The two magma series may have been generated by different degrees of partial melting of the mantle sources with varying water contents. Changes in subduction angle and direction of the paleo-Pacific plate during the Early Cretaceous may have led to lithospheric thinning and upwelling of asthenospheric mantle, which triggered the partial melting of fusible domains of metasomatized lithospheric mantle. The small igneous bodies of the Early Cretaceous shoshonitic to alkaline mafic rocks occur sporadically throughout the southern part of the Korean Peninsula in close spatial association with the Cretaceous basins. They also show crust-like geochemistry and isotopic compositions, similar to the Eopyeong granitoids, implying that the lithospheric thinning-related melting of the metasomatized lithospheric mantle may have been widespread in the southern part of the Korean Peninsula.

Radiogenic Pb mobilization induced by shock metamorphism of zircons in the Apollo 72255 Civet Cat norite clast

In situ U-Pb radiometric dating of zircons is regarded as one of the most widely used and reliable methods to acquire geochronologic ages. However, it has been recently reported that radiogenic Pb (Pb*) mobilization within zircon may, in some cases, cause inaccurate age determinations with no geological significance. Such Pb* mobilization can be caused by deformation, α-coil damage, fluid-assisted annealing, and recrystallization. In this study, we report an investigation of Pb* mobilization in shock metamorphosed lunar zircons. NanoSIMS (nanoscale secondary ion mass spectrometry) and IMS 1280HR ion microprobe dating, EBSD (electron backscatter diffraction) and CL (cathodoluminescence) mapping, and scanning ion imaging (SII) were applied to micro-zircon grains from the Apollo 72255 Civet Cat norite clast. Based on the large number of grains with similarities in internal zoning, habit and trace element geochemistry, and host mineral context, the Civet Cat norite zircons are interpreted to be primary, igneous grains. The chronology obtained for three consecutive surfaces (at different depths) by NanoSIMS, SII, and IMS 1280HR, respectively, indicates that the radiogenic Pb distribution of the Civet Cat norite zircons is heterogeneous among different polished or sputtering surfaces. Forty-two NanoSIMS U-Pb ages (beam size of 5 μm) are concordant on a Wetherill Concordia diagram, and their corresponding 207Pb/206Pb ages spread from 4015 Ma to 4459 Ma. More notably, the six oldest spots of the 42 define a concordant U-Pb age of 4460 ± 31 Ma (2σ, MSWD = 0.47, P = 0.92) and a weighted mean 207Pb/206Pb age of 4453 ± 34 Ma (MSWD = 0.056, P = 0.998). These dates are among the oldest in the lunar highland rocks. However, the 207Pb/206Pb ages of repolished surfaces of these zircons by IMS 1280HR (beam size of 5 μm) do not reproduce the NanoSIMS results (up to 300 Ma younger). The SII (spatial resolution of 2 μm) confirms a heterogeneous distribution of radiogenic Pb within single grains. The EBSD mapping of these zircon grains shows that they have 3–20° of cumulative lattice misorientation. It is proposed that shock-related deformation has facilitated Pb* migration after primordial crystallization. With currently available data, we cannot preclude the possibility that the large errors of the U-Pb ages obscure reverse discordance that would bias our oldest 207Pb/206Pb ages to older values. Conversely, our data could be explained by mixing of Pb-retention and Pb-loss nanodomains as seen in shocked terrestrial zircon such that U-Pb date of 4460 ± 31 Ma approximates the norite formation.

Triple Oxygen Isotope Measurements by Multi-Collector Secondary Ion Mass Spectrometry

Secondary ion mass spectrometry (SIMS) is a powerful technique for in situ triple oxygen isotope measurements that has been used for more than 30 years. Since pioneering works performed on small-radius ion microprobes in the mid-80s, tremendous progress has been made in terms of analytical precision, spatial resolution and analysis duration. In this respect, the emergence in the mid-90s of the large-radius ion microprobe equipped with a multi-collector system (MC-SIMS) was a game changer. Further developments achieved on CAMECA MC-SIMS since then (e.g., stability of the electronics, enhanced transmission of secondary ions, automatic centering of the secondary ion beam, enhanced control of the magnetic field, 1012Ω resistor for the Faraday cup amplifiers) allow nowadays to routinely measure oxygen isotopic ratios (18O/16O and 17O/16O) in various matrices with a precision (internal error and reproducibility) better than 0.5‰ (2σ), a spatial resolution smaller than 10 µm and in a few minutes per analysis. This paper focuses on the application of the MC-SIMS technique to the in situ monitoring of mass-independent triple oxygen isotope variations.

U–Pb zircon eruption age of the Old Crow tephra and review of extant age constraints

Eruption of the Old Crow tephra deposited ~200 km 3 of volcanic ash throughout Alaska and the northwestern Yukon (eastern Beringia), providing an isochronous marker across the region on a scale unique in the Pleistocene. The Old Crow tephra represents a critical temporal piercing point used extensively to link geographically disparate stratigraphic sections and the paleo-environmental records they contain. Although the canonical age of the Old Crow suggests eruption during the transition between the glacial and interglacial periods of Marine Isotope Stages (MIS) 5 and 6 at ~125 ka, recent U–Th–Pb and (U–Th)/He zircon dating of the tephra suggests eruption at ~200 ka, within MIS 7. If accurate, this revised eruption age begets significant change to existing models describing the geologic and biotic evolution of Beringia in the Pleistocene. Thus, confidently knowing the age of the tephra is critical to its time-stratigraphic utility and for past and future work in the region where the tephra has been found. With this contribution, we review existing Old Crow age constraints and present an eruption age for the tephra determined via high spatial resolution ion microprobe U–Pb surface analysis on zircon crystals isolated from source-proximal (<500 km from plausible source) pumiceous pyroclasts of the tephra. By dating only glass-mantled crystals isolated from discrete pumice clasts, we limit the potential for sample contamination from exotic crystals and resulting age bias. The young population of dates from this dataset corroborate previous radiometric dates and confirm Old Crow eruption within late MIS 7 at 207 ± 13 ka.

Zircon U–Pb geochronology and Hf isotope geochemistry of magmatic and metamorphic rocks from the Hida Belt, southwest Japan

Zircon U–Pb and Hf isotope data integrated in this study for magmatic and metamorphic rocks from the Hida Belt, southwest Japan, lead to a new understanding of the evolution of the Cordilleran arc system along the ancestral margins of present-day Northeast Asia. Ion microprobe data for magmatic zircon domains from eight mafic to intermediate orthogneisses in the Tateyama and Tsunogawa areas yielded weighted mean 206Pb/238U ages spanning the entire Permian period (302–254 Ma). Under cathodoluminescence, primary magmatic growth zones in the zircon crystals were observed to be partially or completely replaced by inward-penetrating, irregularly curved featureless or weakly zoned secondary domains that mostly yielded U–Pb ages of 250–240 Ma and relatively high Th/U ratios (> 0.2). These secondary domains are considered to have been formed by solid-state recrystallization during thermal overprints associated with intrusions of Hida granitoids. Available whole-rock geochemical and Sr–Nd isotope data as well as zircon age spectra corroborate that the Hida Belt comprises the Paleozoic–Mesozoic Cordilleran arc system built upon the margin of the North China Craton, together with the Yeongnam Massif in southern Korea. The arc magmatism along this system was commenced in the Carboniferous and culminated in the Permian–Triassic transition period. Highly positive εHf(t) values (> +12) of late Carboniferous to early Permian detrital zircons in the Hida paragneisses indicate that there was significant input from the depleted asthenospheric mantle and/or its crustal derivatives in the early stage of arc magmatism. On the other hand, near-chondritic εHf(t) values (+5 to −2) of magmatic zircons from late Permian Hida orthogneisses suggest a lithospheric mantle origin. Hf isotopic differences between magmatic zircon cores and the secondary rims observed in some orthogneiss samples clearly indicate that the zircons were chemically open to fluids or melts during thermal overprints. Resumed highly positive zircon εHf(t) values (>+9) shared by Early Jurassic granitoids in the Hida Belt and Yeongnam Massif may reflect reworking of the Paleozoic arc crust.

The Ordovician Thores volcanic island arc of the Pearya Terrane from northern Ellesmere Island formed on Precambrian continental crust

Ion microprobe UPb zircon dating of intermediate to felsic rocks coupled with bulk-rock geochemistry analyses and compared to previously published data shows that the Thores Suite of the Pearya Terrane of northern Ellesmere Island (Arctic Canada) represents an Early Ordovician (c. 490–470 Ma) suite formed in an island arc setting. Interestingly, three out of five dated samples contain abundant xenocrystic zircon that have ages spanning from c. 2690 Ma to c. 520 Ma. The vast majority of xenocrystic zircon are Precambrian in age and typical of Laurentia. The youngest well-pronounced age cluster around 580–570 Ma is inferred to be an expression of the Timanide Orogen, traditionally ascribed to Baltica. This geochronological dataset provides new insight on the origin of the Thores Suite of the Pearya Terrane, which was traditionally thought to be formed due to the M'Clintock orogenic event and commonly treated as independent from Caledonian tectonism. We suggest that the Thores island arc formed on a sliver of continental crust within the Iapetus Ocean. The timing of igneous activity recorded by the Thores Suite is consistent with other island arcs and subduction-related metamorphic units that occur within the Caledonides of northern Scandinavia and Svalbard. Hence, we suggest that the Thores volcanic island arc was closely associated with age equivalent arcs developed within the northern Iapetus Ocean. Its juxtaposition with the other successions of the Pearya Terrane is explained by a large-scale, left lateral, strike-slip system operating along the northeastern margins of Baltica and Laurentia, coeval with the main collision between the two continents. This strike-slip system was responsible for the juxtaposition of multiple terranes with contrasting Precambrian histories that can be traced in the present day High Arctic, e.g. in southwest Svalbard and the Pearya Terrane.

Early Permian Granitic Magmatism in Middle Part of the Northern Margin of the North China Craton: Petrogenesis, Source, and Tectonic Setting

The late Palaeozoic was an important period of tectonic evolution for the northern margin of the North China Craton (NCC). The source(s) and tectonic setting of early Permian granitoid rocks emplaced along the northern margin of the NCC are still unclear. These granitoids formed between ~295.4–276.1 Ma (uncertainties ranging from ±1.5 to ±7.8 Ma) according to zircon laser ablation inductively coupled mass spectrometry (LA-ICP-MS) and sensitive high-resolution ion microprobe (SHRIMP) U-Pb data. The Dadongou (DDG) pluton is an A1-type granite and the Dananfangzi (DNFZ) pluton is an A2-type granite. The Erdaowa (EDW), Lisicun (LSC), Wuhai (WH) and Gehuasitai (GHST) plutons are I-type granites. The Yuanbaoshan (YBS) dykes are diorite and syenodiorite. All the granitoids are enriched in large ion lithophile elements and light rare earth elements, depleted in high field strength elements and have negative εNd(t) and εHf(t) values. The A1-type granite was formed by the melting of the mafic crust. The A2-type granite was derived from partial melting of tonalite gneiss from the NCC crust and mantle materials. The EDW, LSC, WH and GHST granites mainly originated from partially melted granulite, with some mantle input. The YBS dykes are formed by the magma mixing of hot mantle melt and the relatively cold crustal magma. The northern margin of the NCC experienced anorogenic and collision tectonic stages, and the structural setting started to transform to post-collision at the later period of early Permian.

Zircon surface crystallization ages for the extremely reduced magmatic products of the Millennium Eruption, Changbaishan Volcano (China/North Korea)

The Millennium Eruption (ME) of Changbaishan volcano (Baitoushan, Paektu) at 946 CE (Common Era) is one of the largest explosive eruptions on Earth during Holocene times. We date unpolished zircon crystal faces from diverse ME products collected from the southern side of Changbaishan volcano where the ME pumice and welded and non-welded pyroclastic flow deposits (PFD) are better exposed. All zircons from a pumice sample of the southern caldera rim and the youngest (Group 1) zircons from a welded pumiceous PFD sample yield an isochron crystallization age of 0.7 ± 1.8 ka (2σ). Zircons from the welded pumiceous PFD sample yield additional two age groups at ~10 ka and ~ 100 ka. Zircons from a non-welded charcoal-containing PFD have only one age population at 100 ka. Our work shows that different eruption products from ME have different zircon surface age distributions and may tap different levels of a zoned felsic magma chamber. In addition, the results indicate that ion microprobe U-Th dating of zircon crystal surfaces from ME pumices can effectively date the Millennium eruption age. Previously reported zircon U-series ages for Qixangzhan eruption (12.2 ± 1.1 ka, 2σ) and Yuanchi eruption (7.3 ± 1.8 ka, 2σ) at Changbaishan are also likely to date their respective eruption ages. The occurrence of 100 ka zircons in welded and non-welded PFDs reveals an important magmatic event for the Changbaishan volcano. Zircon and Fe-rich clinopyroxene crystallized at similar temperature at 770–750 °C, indicative of early zircon crystallization in peralkaline magmas. Another important result is the extremely low oxygen fugacity (fO2 = ΔFMQ-2) of the Changbaishan samples. Minerals in ME magmas were crystallized under some of the most reducing magmatic environments on Earth. Highly reducing conditions of magmas from Changbaishan supports a continental rift setting and argues against significant involvements of subduction-related oxidizing fluids during magma genesis.

Documenting Exhumation in the Central and Northern Menderes Massif (Western Turkey): New Insights from Garnet-Based P-T Estimates and K-Feldspar 40Ar/39Ar Geochronology

AbstractThe Menderes Massif (Turkey) is a metamorphic core complex that records Alpine crustal shortening and extension. Here, nine garnet-bearing schist samples in the Central Menderes Massif (CMM) from below the Alaşehir detachment (AD) were studied to reconstruct their growth history. P-T estimates made using a chemical zoning approach, and petrological observations, indicate garnet grew between ~6 kbar and 550°C and 7.5-9 kbar and 625-650°C. Two P-T path shapes from two samples emerged (isobaric and burial), suggesting that either separate garnet-growth events occurred, or different garnet generations from the same metamorphic event were sampled. Despite observable diffusional modification in most garnets, thermobarometric estimates for crystal-rim growth yield P-T estimates similar to those reported elsewhere in the region. Ion microprobe monazite ages, paired with textural observations, from three of the samples time early retrograde metamorphism (~36-28 Ma). To better understand Neogene extension/exhumation, K-feldspar 40Ar/39Ar ages were obtained from two synextensional granites (Salihli and Turgutlu) exposed along the AD and two from the northern Simav detachment (Koyunoba and Eğrigöz). This data suggests the Simav detachment footwall rapidly exhumed at ~20 Ma, whereas the AD experienced two periods of exhumation/cooling (~14 Ma and~5 Ma). AD ages support a pulsed exhumation model for the massif.

Distribution of Trace Elements Controlled by Sector and Growth Zonings in Zircon from Feldspathic Pegmatites (Ilmen Mountains, the Southern Urals)

The present study contains the detailed ion microprobe data on trace and rare earth elements distribution in the large zircon crystal about 10 × 6 mm in size with distinct growth and sector zonings from Ilmen Mountains feldspathic pegmatite. The zircon crystal morphology is a combination of a prism {110} and a dipyramid {111}. It is found out that the growth sector of the prism {110} generally contains higher concentrations of Th, U, REE, Y, and Nb and exhibits a more gently sloping HREE distribution pattern and a steeper LREE distribution pattern, in contrast to zircon from the growth sector of the dipyramid {111} development. Such a sector zoning pattern was formed at a late stage in crystal growth, when the prism {110} began to prevail over the dipyramid {111}. The zircon studied displays the growth zoning formed of alternating bands in back-scattered electron (BSE) image: wide dark and thin light bands. The last ones contain elevated Th, U, REE, Y, Nb, and Ti concentrations, Th/U ratio and Ce/Ce*. This growth zoning is most probably due to simultaneous crystallization of other minerals that concentrate trace elements, e.g., apatite and monazite, and the lack of equilibrium between zircon and fluid (melt).

High-spatial-resolution measurements of iron isotopes in pyrites by secondary ion mass spectrometry using the new Hyperion-II radio-frequency plasma source.

Iron isotopic signatures in pyrites are considered as a good proxy for reconstructing paleoenvironmental and local redox conditions. However, the investigation of micro-pyrites less than 20 μm in size has been limited by the available analytical techniques. The development of a new brighter radio-frequency plasma ion source (Hyperion-II source) enhances the spatial resolution by increasing the beam density 10 times compared with the Duoplasmatron source. Here we present high-spatial-resolution measurements of iron isotopes in pyrites using a 3 nA-3 μm primary 16 O- beam on two Cameca IMS 1280-HR2 ion microprobe instruments equipped with Hyperion sources at CRPG-IPNT (France) and at SwissSIMS (Switzerland). We tested analytical effects, such as topography and crystal orientation, that could induce analytical biases perceptible through variations of the instrumental mass fractionation (IMF). The δ56 Fe reproducibility for the Balmat pyrite standard is ±0.25‰ (2 standard deviations) and the typical individual internal error is ±0.10‰ (2 standard errors). The sensitivity on 56 Fe+ was 1.2 × 107 cps/nA/ppm or better. Tests on Balmat pyrites revealed that neither the crystal orientation nor channeling effects seem to significantly influence the IMF. Different pyrite standards (Balmat and SpainCR) were used to test the accuracy of the measurements. Indium mounts must be carefully prepared with a sample topography less than 2 μm, which was checked using an interferometric microscope. Such a topography is negligible for introducing change in the IMF. This new source increases the spatial resolution while maintaining the high precision of analyses and the overall stability of the measurements compared with the previous Duoplasmatron source. A reliable method was developed for performing accurate and high-resolution measurements of micrometric pyrites. The investigation of sedimentary micro-pyrites will improve our understanding of the processes and environmental conditions during pyrite precipitation, including the contribution of primary (microbial activities or abiotic reactions) and secondary (diagenesis and/or hydrothermal fluid circulation) signatures.

First Data on the Age (U–Pb, SHRIMP-II) and Composition of Zircon from the Unique Yarega Oil–Titanium Deposit, South Timan

Isotope–geochemical study of zircon from leucoxene–quartz sandstone of the Yarega deposit in South Timan was conducted for the first time using the Sensitive High-Resolution Ion Microprobe II (SHRIMP), Secondary Ion Mass Spectrometer (SIMS) technique. Two groups of zircons were established. The first group has signs of hydrothermal processing with a high content of Light Rare Earth Elements (LREEs), Y, Ca, Sr, and other nonformula elements. Zircon that had been hydrothermal altered from titanium deposits of Middle Timan (Pizhma and Ichet’yu) is characterized by similar geochemical features. The second group of zircons has signs of magmatic genesis, including enrichment in Heavy Rare Earth Elements (HREEs), a positive Ce-anomaly, and a negative Eu-anomaly. The concordant ages of magmatic zircon grains lie in the range of 1100–2100 Ma with maxima around 1230 and 1540 Ma. The age of the magmatic zircon grains indicates the predominance of detrital material in sandstones, which was received during erosion of the ancient Mesoproterozoic basement, and excludes the participation of clastic material from the Timan–Ural folded region.

Quantification of excess 231Pa in late Quaternary igneous baddeleyite

AbstractInitial excess protactinium (231Pa) is a frequently suspected source of discordance in baddeleyite (ZrO2) geochronology, which limits accurate U/Pb dating, but such excesses have never been directly demonstrated. In this study, Pa incorporation in late Holocene baddeleyite from Somma-Vesuvius (Campanian Volcanic Province, central Italy) and Laacher See (East Eifel Volcanic Field, western Germany) was quantified by U-Th-Pa measurements using a large-geometry ion microprobe. Baddeleyite crystals isolated from subvolcanic syenites have average U concentrations of ~200 ppm and are largely stoichiometric with minor abundances of Nb, Hf, Ti, and Fe up to a few weight percent. Measured (231Pa)/(235U) activity ratios are significantly above the secular equilibrium value of unity and range from 3.4(8) to 14.9(2.6) in Vesuvius baddeleyite and from 3.6(9) to 8.9(1.4) in Laacher See baddeleyite (values within parentheses represent uncertainties in the last significant figures reported as 1σ throughout the text). Crystallization ages of 5.12(56) ka (Vesuvius; MSWD = 0.96, n = 12) and 15.6(2.0) ka (Laacher See; MSWD = 0.91, n = 10) were obtained from (230Th)/(238U) disequilibria for the same crystals, which are close to the respective eruption ages. Applying a corresponding age correction indicates average initial (231Pa)/(235U)0 of 8.8(1.0) (Vesuvius) and 7.9(5) (Laacher See). For reasonable melt activities, model baddeleyite-melt distribution coefficients of DPa/DU = 5.8(2) and 4.1(2) are obtained for Vesuvius and Laacher See, respectively. Speciation-dependent (Pa4+ vs. Pa5+) partitioning coefficients (D values) from crystal lattice strain models for tetra- and pentavalent proxy ions significantly exceed DPa/DU inferred from direct analysis of 231Pa for Pa5+. This is consistent with predominantly reduced Pa4+ in the melt, for which D values similar to U4+ are expected. Contrary to common assumptions, baddeleyite-crystallizing melts from Vesuvius and Laacher See appear to be dominated by Pa4+ rather than Pa5+. An initial disequilibrium correction for baddeleyite geochronology using DPa/DU = 5 ± 1 is recommended for oxidized phonolitic melt compositions.

Geochemistry and geochronology of the Jawornik granitoids, Orlica-Śnieżnik Dome, Sudetes, Poland

The Jawornik granitoids intrude, in vein-like form, a sequence of a polymetamorphic metavolcanic and metapelitic rocks of the Orlica-Śnieżnik Dome, Sudetes, Poland. This paper provides whole-rock geochemical data, sensitive high-resolution ion microprobe (SHRIMP) U-Pb zircon geochronological data as well as 40Ar-39Ar age determinations to constrain the genetic and temporal relationships of the different rock types forming these veins. Based on macroscopically visible features of the granitoids and their relationship with tectonic structures visible in the country rocks, four varieties of the Jawornik granitoids have been distinguished: amphibole- and biotite-bearing granites (HBG), biotite-bearing granites (BG), biotite- and muscovite-bearing granites (BMG) and muscovite-bearing granites (MG). The Jawornik granitoids as a whole show a limited but significant variation in major element chemical composition, with SiO2 ranging from 65 to 76 wt.% (average 69.16 wt.%, n = 24). They are subalkalic, peraluminous and calc-alkaline [average A/CNK = 1.07, average (Na2O + K2O) = 7.75, average (Fe2O3t/(Fe2O3t + MgO) = 0.59]. Close inspection of their geochemical parameters showed that the samples investigated can be subdivided into two groups. The first group, the HBG, BG, and BMG varieties, comprising most of the granitoids in the Złoty Stok-Skrzynka Tectonic Zone, were formed by melting of greywackes or/and amphibolites. The MG, belonging to the second group, were formed by partial melting of a more felsic source. The HBG yielded a zircon U-Pb age of 351 ±1.3 Ma and well-defined 40Ar-39Ar plateau ages for hornblende (351.1 ±3.9 Ma) and coexisting biotite (349.6 ±3.8 Ma), indicating probably the oldest magmatic event in this region. Zircons from the MG, the youngest rock variety on the basis of their relationship with the tectonic structures in the host rocks, yielded a U-Pb age of 336.3 ±2.4 Ma, though based on three points only. The biotites and muscovites from the BMG have 40Ar-39Ar plateau ages of 344.1 ±4.7 Ma and 344.6 ±3.8 Ma, respectively. These data, in combination with already published isotopic ages, suggest that the Jawornik granitoids intruded host rocks of the Orlica-Śnieżnik Dome in three stages, at ~350, ~344 and ~335 Ma.

Strontium isotope analysis of apatite via SIMS

We report the development of a SIMS analytical method for in situ Sr isotope analysis of the mineral apatite at an analytical scale of 15 μm or less. Experiments were conducted on a series of reference apatites of widely differing Sr contents at three different mass resolution settings: low (3000), moderate (4200) and very high (16000), using a large-geometry CAMECA 1280 ion microprobe retrofitted with a HyperionTM oxygen plasma ion source. Peak-stripping algorithms tailored to the different mass-resolution settings were developed to correct for significant interferences on the target strontium isotope species in the mass spectra, namely Ca dimers, CaPO, Rb and SrH, and for instrumental mass fractionation. The most consistently accurate and precise 87Sr/86Sr ratios were achieved at the 3000 mass resolution setting with appropriate energy filtering and use of a cold trap. On average, corrected 87Sr/86Sr ratios by this method were elevated by ~0.8‰ above equivalent TIMS and solution ICPMS data, with consistent behaviour across the range of Sr concentrations. Individual spot precision of ± 0.001 to 0.004 (2SE) was achieved, depending on Sr content. The key advantages of SIMS analysis compared to existing LA-MC-ICP-MS methods are the high spatial resolution, low sample consumption, and the high mass resolution that allows for the elimination of problematic isobaric interferences. Our approach is particularly useful for the analysis of small or valuable targets, such as mineral inclusions or meteoric samples, and for apatite with high REE contents. However, the much larger volume of material consumed during LA-MC-ICP-MS analysis allows for substantially better precision than the SIMS method presented here. The highly variable trace element composition of natural apatites, involving both cationic and anionic substitutions, necessitates careful characterisation of prospective targets prior to any in situ analysis, in addition to matching to appropriate reference materials.

Current and emerging analytical techniques for geochemical and geochronological studies

Progress in both basic and applied geochemical studies highly depend on the progress of the analytical instrumentation in general. In recent times, there have been spectacular developments in different instrumental analytical techniques used for accurate determinations of elemental/isotopic abundances from per cent levels to pg/g levels in a variety of geological materials. Some of the important instrumental analytical techniques which are currently in use for geochemical studies include atomic absorption spectrometry (AAS), inductively coupled plasma atomic emission spectrometry (ICP‐AES), recently introduced microwave plasma‐atomic emission spectroscopy (MP‐AES), X‐ray fluorescence spectrometry (XRF), instrumental neutron activation analysis (INAA), inductively coupled plasma mass spectrometry (ICP‐MS), ICP‐time of flight mass spectrometry (ICP‐TOF‐MS), high resolution inductively coupled plasma mass spectrometry (HR‐ICP‐MS), and multi‐collector‐ICP‐MS (MC‐ICP‐MS), with each one having its own merits and the limitations. Developments in sensitive high‐resolution ion microprobe (SHRIMP) opened up zircon geochronology and has revolutionized age dating of rocks byin‐situisotopic analysis on single mineral grains such as zircons. Recently emerged MC‐ICP‐MS in combination with collision/reaction cell is allowing detection of small variations in natural isotopic compositions of non‐traditional stable isotopes. Advancements in other microanalytical techniques such as laser ablation‐ICP‐MS (LA‐ICP‐MS), electron probe micro‐analyser (EPMA), scanning electron microscopy and energy dispersive X‐ray spectroscopy (SEM‐EDS), laser‐induced breakdown spectroscopy (LIBS), have markedly improved direct solid analysis,in‐situprobing of individual minerals, fluids, and melt inclusions. Raman spectroscopy is currently emerging as a powerful geochemical analytical tool. Some interesting combination instruments such as ICP‐MS/AES showed synergic benefits when used in geochemical studies. There is also substantial progress in other critical areas such as sample preparation, sample decomposition, development of geochemical reference materials, and quality issues in general. Miniaturization is perhaps the most notable current trend in analytical techniques, and their use in exploration studies provide near‐real time sampling guidance in the field. In this review, all these aspects are updated, summarized and discussed at depth with practical examples. However, most of these instruments are expensive and complex and future developments may focus on some of the drawbacks of the current systems to realize their full potential for geochemical/geochronological studies.